Method for preparing cigarette catalyst by utilizing waste, product and application thereof
By using the catalyst prepared by waste as tobacco additives, the problems of high cost and great taste in the prior art are solved, and the content of harmful components in the combustion process of cigarettes is reduced at low cost and low toxicity, and the taste of cigarettes is improved. Burning process.
Patent Information
- Application Number
- CN202411004470.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-25
- Publication Date
- 2024-12-13
AI Technical Summary
While reducing the combustion temperature and tar release, existing cigarette catalysts have high costs and great impact on taste. The cost of industrial synthesis of zeolites is high, which limits its wide application.
Use waste such as fly ash, waste heating heating patches, etc. as raw materials to prepare catalysts by mixing with NaOH and potassium citrate and grinding of zirconium oxide grinding balls. As tobacco additives, selectively during the combustion process of cigarettes through surface modification. Catalyze the reduction of harmful components.
It achieves low-cost and low-toxicity reduction of harmful components during the combustion process of cigarettes, maintains the nicotine content of flue gas, improves the taste and combustion process of cigarettes, and reduces the tar content.
Smart Images
Figure BDA0004962600390000091 
Figure BDA0004962600390000101 
Figure BDA0004962600390000102
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of traditional cigarette combustion, and in particular relates to a method for preparing a cigarette catalyst by utilizing waste, and a product and application thereof. Background Art
[0002] It is reported that catalysts such as molecular sieves, mesoporous materials, metal oxides and alkali / alkaline earth metals are active in the process of biomass pyrolysis and can effectively change the combustion process of cigarettes. Potassium salts, as a commonly used metal salt additive, can reduce the combustion temperature of cigarettes, and the release of tar and particulate matter is also reduced accordingly. However, in the process of sensory evaluation, the addition of potassium salts will affect the taste of cigarettes, while the effects of other metal salts such as sodium salts and alkaline earth metals in reducing tar and harm are worse than those of potassium salts.
[0003] Although current studies have proven that other materials have the characteristics of reducing tar and harm, they focus on reducing tar and harm while using expensive catalysts, or they are toxic and affect the sensory organs, which limits their widespread application. The diverse microporous structures of molecular sieves give molecular sieves diverse catalytic properties. At the same time, the confined space of the cage and pore structure inside the molecular sieve can also effectively regulate the intermediates of the catalytic reaction, and has shown good effects in catalytic processes such as alkylation, aromatization and etherification. Compared with others, molecular sieves have stronger adsorption, adjustable acidity and alkalinity, and shape selectivity of the pores. Unmodified molecular sieves have been proven to reduce the tar content in the cigarette combustion process by adding them to tobacco shreds, and remove aromatic compounds and nitrosamines in mainstream smoke.
[0004] However, although catalytic materials such as molecular sieves have a certain adsorption effect, the combustion process of cigarettes determines that the catalyst added to tobacco has a shorter service life than other catalysts. Industrially synthesized zeolites mainly use chemical reagents as raw materials, which have high preparation costs and therefore high use costs. Therefore, it is necessary to find cheap raw materials to reduce the synthesis cost of molecular sieves. Clean and efficient energy and resource utilization of solid waste is a key point advocated by the country. The low-cost and harmless utilization of biomass ash is a part of the utilization of solid waste resources. Using biomass ash as raw material can effectively prepare low-cost, high-performance synthetic zeolites of molecular sieves, which can reduce the preparation cost of zeolite and is a high-value utilization method with application prospects. Summary of the invention
[0005] In view of the deficiencies of the prior art, the object of the present invention is to provide a method for preparing a cigarette catalyst using waste, and a product and application thereof.
[0006] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:
[0007] In a first aspect, the present invention provides a method for preparing a cigarette catalyst using waste, the method comprising:
[0008] (1) mixing NaOH, waste, potassium citrate and water to obtain a suspension;
[0009] (2) grinding the suspension to separate the solid from the liquid, and then collecting the solid matter;
[0010] (3) drying the solid to obtain the catalyst;
[0011] The waste includes any one of fly ash, waste heating pads, gasification ash or blast furnace slag, or a combination of at least two of them.
[0012] The present invention uses a catalyst prepared from waste as a tobacco additive to participate in the combustion process of cigarettes, and realizes the selective catalysis of harmful components in cigarette smoke through surface modification, effectively reducing other harmful components without changing the nicotine content in mainstream smoke or when the change in mainstream nicotine content is similar to that produced by untreated tobacco.
[0013] Preferably, the solid-to-liquid ratio of NaOH to water in step (1) is 40-120 g / L, for example, 50 g / L, 60 g / L, 70 g / L, 80 g / L, 90 g / L, 100 g / L or 110 g / L.
[0014] Preferably, the waste in step (1) includes fly ash and discarded heating pads.
[0015] Preferably, the mass ratio of the fly ash and the discarded heating pad is 1:(0.5-2), for example, it can be 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8 or 1:1.9, etc.
[0016] Preferably, the mass ratio of NaOH, waste and potassium citrate in step (1) is (0.4-1):(1-4):(1-2).
[0017] Wherein "0.1-1" can be 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, etc.;
[0018] “1-4” can be 1.1, 1.3, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, 3.3, 3.5 or 3.8, etc.;
[0019] “1-2” can be 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8 or 1.9, etc.
[0020] Preferably, the mixing temperature in step (1) is 50-60°C, for example, it can be 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C or 59°C.
[0021] Preferably, the grinding in step (2) is carried out in a ball mill.
[0022] Preferably, the grinding speed is 300-600 rpm, for example, 310 rpm, 330 rpm, 350 rpm, 380 rpm, 400 rpm, 420 rpm, 450 rpm, 480 rpm, 500 rpm, 520 rpm, 550 rpm or 580 rpm, etc.
[0023] Preferably, the grinding time is 1-2 h, for example, it can be 1.1 h, 1.2 h, 1.3 h, 1.4 h, 1.5 h, 1.6 h, 1.7 h, 1.8 h or 1.9 h, etc.
[0024] Preferably, zirconium oxide grinding balls are added to the ball mill jar.
[0025] Preferably, the amount of the zirconium oxide grinding balls added is 10-15 times the total amount of the waste, for example, 11 times, 12 times, 13 times or 14 times, etc.
[0026] Preferably, the drying temperature in step (3) is 100-110°C, for example, it can be 101°C, 102°C, 103°C, 104°C, 105°C, 106°C, 107°C, 108°C or 109°C, etc.
[0027] Preferably, the drying time is 10-15 h, for example, 10 h, 11 h, 12 h, 13 h, 14 h or 15 h.
[0028] In a second aspect, the present invention provides a combustion catalyst for cigarettes, and the combustion catalyst for cigarettes is prepared by the method described in the first aspect.
[0029] In a third aspect, the present invention provides a use of the cigarette combustion catalyst as described in the second aspect in a traditional cigarette.
[0030] In a fourth aspect, the present invention provides a traditional cigarette, wherein the traditional cigarette comprises a tobacco segment and a filter segment;
[0031] The tobacco shreds are added with the cigarette combustion catalyst as described in the second aspect.
[0032] Preferably, the dosage of the cigarette combustion catalyst is 0.15-0.3 g / cigarette, for example, 0.18 g / cigarette, 0.20 g / cigarette, 0.22 g / cigarette, 0.24 g / cigarette, 0.26 g / cigarette or 0.28 g / cigarette.
[0033] The numerical range described in the present invention not only includes the point values listed above, but also includes any point values between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range.
[0034] Compared with the prior art, the present invention has the following beneficial effects:
[0035] (1) The raw materials used in the preparation method provided by the present invention are low-cost, which can not only realize the recycling of waste and effectively save energy, but also has simple steps. The prepared catalyst does not change the nicotine content in the mainstream smoke or when the change in mainstream nicotine content is similar to that produced by untreated tobacco, and effectively reduces other harmful components.
[0036] (2) The cigarette combustion catalyst provided by the present invention is a substance that can significantly reduce the reaction energy barrier without changing the total standard Gibbs free energy of the reaction, allowing the reaction to occur under relatively mild conditions. It can effectively change the cigarette combustion process to achieve the effect of reducing tar and reducing harm. DETAILED DESCRIPTION
[0037] In order to further explain the technical means and effects adopted by the present invention, the technical solution of the present invention is further described below in conjunction with the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.
[0038] The raw materials described in the present invention can be used as long as they are purchased from regular dealers.
[0039] Example 1
[0040] This embodiment provides a combustion catalyst for cigarettes, and the preparation method of the combustion catalyst for cigarettes is as follows:
[0041] (1) NaOH, waste (fly ash and waste heating pad material in a mass ratio of 1:0.5), potassium citrate and water (solid-to-liquid ratio with NaOH of 80 g / L) in a mass ratio of 0.6:2:1 were mixed at 55° C. to form a suspension;
[0042] (2) adding the suspension into a grinding jar containing zirconium oxide grinding balls, grinding the suspension for 1.5 hours at a speed of 500 rpm in a forward and reverse rotation alternating manner, wherein the mass ratio of the zirconium oxide grinding balls to the waste is 12:1. After grinding, the suspension is centrifuged to separate the solid matter;
[0043] (3) Dry the solid at 105°C for 12 hours to obtain the product.
[0044] Example 2
[0045] This embodiment provides a combustion catalyst for cigarettes, and the preparation method of the combustion catalyst for cigarettes is as follows:
[0046] (1) NaOH, waste (fly ash and waste heating pad material in a mass ratio of 1:1), potassium citrate and water (solid-to-liquid ratio with NaOH of 60 g / L) in a mass ratio of 0.8:1:1 were mixed at 60° C. to form a suspension;
[0047] (2) adding the suspension into a grinding jar containing zirconium oxide grinding balls, grinding the suspension for 2 h at a speed of 300 rpm in a forward and reverse rotation, wherein the mass ratio of the zirconium oxide grinding balls to the waste is 10:1. After grinding, the suspension is centrifuged to separate the solid matter;
[0048] (3) Dry the solid at 110°C for 10 h to obtain the product.
[0049] Example 3
[0050] This embodiment provides a combustion catalyst for cigarettes, and the preparation method of the combustion catalyst for cigarettes is as follows:
[0051] (1) NaOH, waste (fly ash and waste heating pad material in a mass ratio of 0.5:1), potassium citrate and water (solid-liquid ratio with NaOH is 100 g / L) in a mass ratio of 0.8:4:1 are mixed at 50° C. to form a suspension;
[0052] (2) adding the suspension into a grinding jar containing zirconium oxide grinding balls, grinding the suspension at 600 rpm in a forward and reverse rotation for 1 h, wherein the mass ratio of the zirconium oxide grinding balls to the waste is 15:1. After grinding, the suspension is centrifuged to separate the solid matter;
[0053] (3) Dry the solid at 100°C for 15 hours to obtain the product.
[0054] Example 4
[0055] This embodiment provides a combustion catalyst for cigarettes. The preparation method of the combustion catalyst for cigarettes is different from that of Example 1 only in that in step (1), the mass ratio of NaOH, waste and potassium citrate is 2:1:3, and the amount of water and the composition of the waste are kept unchanged. The other steps and parameters are consistent with those of Example 1.
[0056] Example 5
[0057] This embodiment provides a combustion catalyst for cigarettes. The preparation method of the combustion catalyst for cigarettes is different from that of Example 1 only in that the mass ratio of NaOH solution, waste and potassium citrate in step (1) is 0.1:5:1, and the amount of water and the composition of the waste are kept unchanged. The other steps and parameters are consistent with those of Example 1.
[0058] Example 6
[0059] This embodiment provides a combustion catalyst for cigarettes. The preparation method of the combustion catalyst for cigarettes is different from that of embodiment 1 only in that the grinding balls in step (2) are cerium oxide grinding balls and the amount of grinding balls is kept unchanged. The other steps and parameters are consistent with those of embodiment 1.
[0060] Example 7
[0061] This embodiment provides a combustion catalyst for cigarettes. The preparation method of the combustion catalyst for cigarettes is different from that of Embodiment 1 only in that the mass ratio of the zirconium oxide grinding balls to the waste in step (2) is 18:1, and the other steps and parameters are consistent with those of Embodiment 1.
[0062] Example 8
[0063] This embodiment provides a combustion catalyst for cigarettes. The preparation method of the combustion catalyst for cigarettes is different from that of Embodiment 1 only in that the mass ratio of the zirconium oxide grinding balls to the waste in step (2) is 5:1, and the other steps and parameters are consistent with those of Embodiment 1.
[0064] Comparative Example 1
[0065] This comparative example provides a combustion catalyst for cigarettes, and the preparation method of the combustion catalyst for cigarettes is as follows:
[0066] (1) NaOH in a mass ratio of 0.6:2, waste (fly ash and waste heating pad material in a mass ratio of 1:0.5), and water (solid-to-liquid ratio with NaOH of 80 g / L) were mixed at 55° C. to form a suspension;
[0067] (2) adding the suspension into a grinding jar containing zirconium oxide grinding balls, grinding the suspension for 1.5 hours at a speed of 500 rpm in a forward and reverse rotation alternating manner, wherein the mass ratio of the zirconium oxide grinding balls to the waste is 12:1. After grinding, the suspension is centrifuged to separate the solid matter;
[0068] (3) Dry the solid at 105°C for 12 hours to obtain the product.
[0069] Comparative Example 2
[0070] This comparative example provides a combustion catalyst for cigarettes, and the preparation method of the combustion catalyst for cigarettes is as follows:
[0071] (1) Mixing 1 mol / L waste (mass ratio of fly ash and waste heating pad material is 1:0.5) with a mass ratio of 2:1, potassium citrate and water (the amount used is the same as in Example 1) to obtain a mixture;
[0072] (2) adding the mixture into a grinding jar containing zirconium oxide grinding balls, grinding the mixture in a forward and reverse rotation at a speed of 500 rpm for 1.5 hours, wherein the mass ratio of the zirconium oxide grinding balls to the waste is 12:1, and obtaining a solid after grinding;
[0073] (3) Dry the solid at 105°C for 12 hours to obtain the product.
[0074] Comparative Example 3
[0075] This comparative example provides a combustion catalyst for cigarettes, and the preparation method of the combustion catalyst for cigarettes is as follows:
[0076] (1) adding waste (fly ash and waste heating pad materials in a mass ratio of 1:0.5) into a grinding pot containing zirconium oxide grinding balls, and grinding for 1.5 hours at a speed of 500 rpm in a forward and reverse alternating manner, wherein the mass ratio of the zirconium oxide grinding balls to the waste is 12:1, and obtaining a solid after grinding;
[0077] (2) Dry the solid at 105°C for 12 hours to obtain the product.
[0078] Application Example 1:
[0079] This application example provides a cigarette, which includes a tobacco shred segment and a filter segment. The cigarette combustion catalyst of Example 1 is sprayed on the tobacco shreds, with an amount of 0.2 g / cigarette, and the cigarette is prepared on a machine after being evenly mixed.
[0080] Application Example 2-8
[0081] This application example provides 8 kinds of cigarettes. The only difference between the cigarettes and application example 1 is that the catalyst of example 1 is replaced by the catalysts of examples 2-8 in equal amounts. The structure of the cigarettes is consistent with that of application example 1.
[0082] Comparative Application Examples 1-3
[0083] This comparative application example provides three kinds of cigarettes. The difference between the cigarettes and application example 1 is that the catalyst of example 1 is replaced by the catalysts of comparative examples 1-3 in equal amounts. The structure of the cigarettes is consistent with that of application example 1.
[0084] Test Example 1 Comparison of harmful chemical components released in flue gas
[0085] The cigarettes obtained from Application Examples 1-8 and Comparative Application Examples 1-3 were used as test cigarettes, and cigarettes without any other ingredients added were used as control cigarettes. The smoke captured by the test cigarettes and the control cigarettes was tested for the release of harmful chemical components.
[0086] Test method:
[0087] The tar content is determined by using a conventional analysis smoking machine for cigarettes in accordance with GB / T 19609-2004 for total particulate matter and tar;
[0088] The CO content refers to GB / T 23356-2009 Determination of carbon monoxide in the gas phase of cigarette smoke - non-scattering infrared method;
[0089] The HCN content is based on the continuous flow method for determination of hydrocyanic acid in mainstream cigarette smoke in YC / T 253-2008;
[0090] The NNK content is based on GB / T 23228-2008 Determination of tobacco-specific N-nitrosamines in total particulate matter in mainstream cigarette smoke by gas chromatography-thermal analysis;
[0091] The ammonia content is based on the determination of ammonia in mainstream cigarette smoke by ion chromatography according to YC / T 377-2010;
[0092] The benzo[a]pyrene content refers to GB / T 21130-2007 Determination of benzo[a]pyrene in total particulate matter in cigarette smoke;
[0093] The phenol content is determined by high performance liquid chromatography according to YC / T 255-2008;
[0094] The crotonaldehyde content is determined by high performance liquid chromatography according to YC / T 254-2008, a method for determining main carbonyl compounds in mainstream cigarette smoke.
[0095] The results are shown in Tables 1 and 2 below.
[0096] Table 1
[0097]
[0098]
[0099] Table 2
[0100]
[0101] It can be seen from the data in Tables 1 and 2 that the content of harmful chemical components in cigarette smoke after the cigarette combustion catalyst obtained by the present invention is used is lower, and the material-liquid ratio of NaOH solution to waste, potassium citrate, and the mass ratio of zirconium oxide grinding balls to waste in the preparation process will affect the adsorption effect of the catalyst.
[0102] Test Example 2 Sensory Evaluation
[0103] The cigarettes obtained in Application Examples 1-8 and Comparative Application Examples 1-3 were used as test cigarettes, and cigarettes without any other ingredients added were used as control cigarettes for sensory evaluation.
[0104] Organize 7 tasters to evaluate and score the food according to the evaluation contents and criteria in Table 3-4. The sensory quality indicators are scored on a 100-point scale.
[0105] The sensory quality evaluation indicators are: smoke volume (referring to smoke concentration and consistency), aroma and fragrance, strength, harmony, irritation and taste (aftertaste); the specific definitions of the six sensory quality evaluation indicators are shown in Table 3, and the evaluation criteria of the six sensory quality evaluation indicators are shown in Table 4.
[0106] Table 3
[0107]
[0108] Table 4
[0109]
[0110] The specific results are shown in Table 5:
[0111] Table 5
[0112] sample Smoke volume aroma Momentum coordination Irritant Taste Total score Application Example 1 8.2 27.8 8.8 9.6 12.8 23.8 91 Application Example 2 8.1 27.4 8.7 9.5 13.7 23.9 91.3 Application Example 3 8.4 26.7 7.8 9.4 13.8 24.3 90.4 Application Example 4 6.5 26.6 7.1 8.2 12.9 22.8 84.1 Application Example 5 6.7 25.9 7.3 8.5 11.9 20.7 81 Application Example 6 6.9 25.1 7.7 8.9 11.6 19.8 80 Application Example 7 6.5 25.8 7.5 8.6 11.8 19.9 80.1 Application Example 8 6.3 25.6 7.5 8.2 10.9 19.8 78.3 Comparative application example 1 6.2 25.9 7.3 8.1 10.6 18.6 76.7 Comparative Application Example 2 6.1 25.8 7.4 8.2 10.3 18.6 76.4 Comparative Application Example 3 6.2 26.2 7.2 8.8 10.2 18.1 76.7 Control cigarettes 5.4 24.1 6.9 8.2 9.2 17.0 70.8
[0113] It can be seen from the data in Table 5 that after adding the catalyst for cigarettes of the present invention, not only the smoke volume is larger, the smoke aroma is stronger, fuller and softer, but also the throat irritation can be effectively reduced and the aftertaste in the mouth is improved.
[0114] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the method for preparing a cigarette catalyst from waste, its products and applications, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.
[0115] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.
[0116] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.
Claims
1. A method for preparing a cigarette catalyst using waste, characterized in that: The method comprises: (1) mixing NaOH, waste, potassium citrate and water to obtain a suspension; (2) grinding the suspension to separate the solid from the liquid, and then collecting the solid matter; (3) drying the solid to obtain the catalyst; The waste includes any one of fly ash, waste heating pads, gasification ash or blast furnace slag, or a combination of at least two of them.
2. The method according to claim 1, characterized in that The solid-to-liquid ratio of NaOH to water in step (1) is 40-120 g / L; Preferably, the waste in step (1) includes fly ash and discarded heating pads.
3. The method according to claim 1 or 2, characterized in that The mass ratio of NaOH, waste and potassium citrate in step (1) is (0.4-1):(1-4):(1-2); Preferably, the mixing temperature in step (1) is 50-60°C.
4. The method according to any one of claims 1 to 3, characterized in that The grinding in step (2) is carried out in a ball mill; Preferably, the rotation speed during grinding is 300-600 rpm; Preferably, the grinding time is 1-2h.
5. The method according to claim 4, characterized in that The ball milling jar contains zirconium oxide grinding balls; Preferably, the amount of the zirconium oxide grinding balls added is 10-15 times the total amount of waste.
6. The method according to any one of claims 1 to 5, characterized in that The drying temperature in step (3) is 100-110° C. Preferably, the drying time is 10-15 hours.
7. A combustion catalyst for cigarettes, characterized in that: The cigarette combustion catalyst is prepared by the method according to any one of claims 1 to 6.
8. Use of the cigarette combustion catalyst as claimed in claim 7 in traditional cigarettes.
9. A traditional cigarette, characterized in that: The traditional cigarette comprises a tobacco segment and a filter segment; The tobacco shreds are added with the cigarette combustion catalyst as claimed in claim 7.
10. The traditional cigarette according to claim 9, characterized in that: The dosage of the combustion catalyst for cigarettes is 0.15-0.3 g / cigarette.